Method for producing defined layers or layer systems

ABSTRACT

The invention relates to a method for producing defined layers or layer systems made of polymers or oligomers on any solid surface and with a controlled structure, according to which the layers are chemically deposited on the solid surface by means of live/controlled free-radical polymerization. Said method comprises the following steps: a) bonding the compounds of the general formula (a) A—L—I to the solid surface via the active group A where A represents an active group, I is the initiating group for ATRP polymerization and L is the binding link between A and I; b) carrying out live/controlled free-radical polymerization by reacting the initiator group I with monomers, macromonomers or mixtures able to undergo free-radical polymerization, which produces the polymer layer on the solid surface. The invention also relates to solid surfaces with oligomer or polymer layers and initiators for carrying out the method.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention concerns a process for producing defined layers or layersystems of polymers or oligomers on any solid surface, with a controlledstructure, wherein each layer is chemically deposited on the solidsurface by means of a “living”/controlled radical reaction. Theinvention further concerns solid surfaces provided with oligomer orpolymer layers, as well as various compounds with an anchor group aswell as a group or functionality from which polymerization growth occursaccording to the ATRP mechanism. These types of compounds are referredto in the following as initiators.

The present invention concerns a process based upon this mechanism of“living”/controlled radical reaction and polymerization for chemicalmodification of various solid surfaces. The solid substrate could be ofany freely selected material, could be solid or porous, could be finelyspread, could be of natural or synthetic origin, or exhibit aheterogeneous surface structure or heterogeneous surface composition.The physical-mechanical characteristics of the utilized solid substrateare not of consequence in the process, nor are hardness, ductility,deformability or surface roughness.

The term “surface” herein is not limited to the outer surface. in theconventional sense, where it is generally understood to mean theboundary between the solid and the gas or liquid environment. Thepresent invention is equally applicable to internal surfaces of a porousmaterial. Beyond this, when using the inventive surface modifyingmaterials, the term “surface” is also intended to refer in general tovarious phase boundaries. Thus the surface could also be, for example,an interface between two different components of a composite material.Examples of this type include composites of a polymer matrix and aninorganic reinforcing agent, a polymer filled with a dyestuff, or apolymer-metal composite; generally also included are composites of apolymer matrix and a functional additive.

The surface characteristics of the solid substrate can be tailored bychemical modification to meet requirements. On the one hand, a desiredquality can be imparted to the surface; on the other hand, the qualityof the physical interactivity of the surface modified solid to othermaterials, the chemical reactivity, and the ability to form chemicalbonds with other materials can be adjusted as required.

If layers or layer systems are applied to the surface, then in certaincases the characteristics of the original surface can be so changed,that the characteristics of the system as a whole will be influencedonly by the coating. Thus it is possible, for example, to provide acomposite material with mechanical stability by selecting a suitablecarrier or backbone material, and on the other hand to adjust thedesired mechanical, physical and/or chemical characteristics of thesurface by using the layer system.

2. Description of the Related Art

In order to modify solid surfaces by application of polymers, varioustechniques could be employed. Processes are described in the literature,in which dissolved polymers are sprayed, spin-coated, dip-coated orapplied according to the Langmuir-Blodgett-Technique (LB-films). Thebonding of the polymers to the surface therewith almost exclusively isof an adhesive nature. The process parameters frequently are difficultto control when using these processes; in addition, particularly in thecase of the Langmuir-Blodgett-Technique, this only can be employed onplanar surfaces and substantially is limited to amphiphilic or rigidchain molecules.

Polymer molecules also can be bonded to the solid surface chemically, byforming a covalent chemical bond with the solid surface via mostlyterminal groups of the polymer molecules (“grafting-to”, for example viaa condensation reaction). One disadvantage of this process is that theyield with this type of surface reaction, and therewith the graftdensity of the polymer molecules upon the surface, generally is not veryhigh since previously bonded polymer molecules hinder the approach ofsubsequent molecules to the surface. Further, the process is limited topolymers with relatively low molar mass, since only with small moleculesthere is a sufficiently high probability that the functional group ofthe polymer molecule is within the reach of the bonding sites on thesolid surface and thus a chemical reaction between the two would bepossible.

In order to circumvent the disadvantages associated with“grafting-to”-processes, in accordance with further developed processesthe polymer reaction for forming the polymers is initiated or triggereddirectly on the solid surface (“grafting-from”) [J. Rühe,“Massgeschneiderte Oberflächen”, Nachr. Chem. Tech. Lab. 42 (1994)1237]. Therein, in the state of the art for polymerization reactionsbeginning with solid materials, the classical radical grafting reactionis generally described: for initiating the radical polymerizationreaction conventional initiators are employed, that is, azo compounds,peroxide, among others. If one attaches this type of initiatorcovalently to the solid surface in order to thereby initiate thegrafting reaction, this is associated with the following disadvantage:in symmetrical initiators such as for example azo-bis-isobutyro-nitrile(AiBN) or benzoyl peroxide (BPO) there is, after decomposition, onefragment covalently bonded to the solid as initiating radical, thesecond radical fragment remains unbound and can for its part initiate apolymerization reaction, which however does not occur on the solidsurface, but rather unbound. In a polymerization solution with the abovementioned covalent initiators there is thus formed, besides the boundpolymer, always also non-bound polymer.

This situation has lead thereto, that an alternative path has beensought using asymmetric initiators in which, after decomposition, theunbound radical fragment has essentially no reaction initiating effect.This is described in detail for example in the writings of Rühe et al.[O. Prucker, J. Rühe, Macromolecules 31, 592 (1998); O. Prucker, J.Rühe, Macromolecules 31, 602 (1998)].

In addition to this, all until now conventionally initiated radicalpolymerization reactions are subjected to the classical kinetics ofradical polymerization, that is, the graft branch length and thetermination reactions can only be insufficiently controlled and thechain length is subjected to the typical chain length distribution ofclassical radical polymerization [s. Bruno Vollmert, Grundriss derMakromolekularen Chemie, Bd. I, E. Vollmert-Verlag, Karlsruhe, 1979].Further, the chain ends of the graft branches are no longer reactiveafter the polymerization reaction, so that for example an additionalpolymerization for a second generation of polymer is not possible.

This disadvantage of radical polymerization was overcome in large partrecently by a new process. If a radical polymerization reaction iscarried out using a “living”/controlled radical mechanism, then definedpolymers can be produced, of which the chain length and polydispersitycan be controlled substantially better than in the case of classicalradical polymerization. Since the number of the chain terminations inthis process is strongly reduced, the term “stable free radicalpolymerization” (SFRP) is also employed. This process experienced afurther refinement, as taught by K. Matyjaszewski et al., by theintroduction of the concept of the “atom transfer radicalpolymerization” (ATRP) [K. Matyjaszewski, S. Coca, S. Gaynor, Y.Nakagawa, S. M. Jo, “Preparation of Novel Homo- and Copolymers usingAtom Transfer Radical Polymerization”, WO 98/01480]. “Living”/controlledradical polymerizations, also in their refinement according to theATRP-mechanism, have until now only been carried out in the liquidphase, with or without supplemental solvent.

Craig J. Hawker et al. describe in ACS Polym. Preprints [Div. Polym.Chem. (39), 626 (1998)] the synthesis and application of polymers withutilization of “living” radical polymerization reactions. As initiatorsfor the radical polymerization, compounds are employed which contain anitroxide group. These compounds generally exhibit terminaltrichlorosilyl groups which can be bound to surfaces of silica gel andsilica wafers by chemical reaction.

Tsujii et al. in Macromolecules 1998, 31, 5934 describe controlled graftpolymerization of methyl methacrylate on silicon oxide containingsubstrates by the combined use of the Langmuir-Blodgett-(LB)-Techniqueand the ATRP Technique (Atom Transfer Radical Polymerization). Asinitiator compound 2-(4-chlorosulfonylphenyl)-ethyltrimethoxysilane isused. This compound possesses a chlorosulfonyl group as initiator groupfor the “living”/controlled polymerization. After depositing a monolayerof the above mentioned initiator, which had been compressed on awater/air interface by means of LB-Technique, on a silicon wafer, the“living”/controlled radical polymerization of methyl methacrylate iscarried out on this modified surface.

These processes according to the state of the art exhibit the followingdisadvantages: In the “stable free radical polymerization” SFRP with useof nitroxides it often occurs that, due to the necessarily hightemperatures of 120 to 130° C., frequently simultaneously thermalpolymerization reactions proceed, which do not initiate at the surface.Therewith substantial disadvantages are associated with the process forthe “living”/controlled radical grafting of solid surfaces, namely

a) the production of unbound polymer consumes monomer,

b) the growing bonded as well unbonded polymer chains compete fornitroxide and influence therewith the control of the growing chains,

c) unbonded polymer is present as reaction product, besides the polymermodified solid surface.

According to the publication of Tsujii et al.,2-(4-chlorosulfonylphenyl)-ethyltrimethoxysilane is employed asinitiator compound. Chlorosulfonylphenyl groups are known to be highlyreactive and in particular sensitive to hydrolysis, so that they aredifficult to work with. Compounds which exhibit such groups, includingthe therewith modified surface, are unstable.

Further the LB-method described in this publication can only be appliedto planar substrate surfaces, and this on limited surface areas and not,however, on solid surfaces of any size, shape and composition, as wellas not on materials with open pores on their surfaces. The density ofthe molecules on the layer can only be incompletely influenced. Thetesting of the degree of polymerization of the grafted-on polymermolecules is only carried out indirectly, the grafted-on polymermolecules themselves are not involved therein. Further, it is notachieved that the chain ends are capable of further initiation.

SUMMARY OF THE INVENTION

This technical task is solved by a process for production of definedlayers or layer systems of polymers or oligomers with controlledstructure on any solid surface, wherein the layers are depositedchemically on the solid surface by means of “living”/controlled radicalreactions, by the following steps:

a) bonding compounds of the general formula

A—L—I  (1)

 to the solid surface via the anchor group A, where A represents ananchor group, I is the initiating group for ATRP polymerization, and Lis the linkage between A and I.

b) carrying out “living”/controlled free radical polymerizationaccording to the ATRP-mechanism by reacting the initiator group I boundto the solid surface with monomers, macromonomers or mixtures able toundergo free radical polymerization, which produces the polymer layer onthe solid surface.

The invention concerns a process which employs “living”/controlledradical polymerization for simultaneous and defined chemicalmodification of any solid surfaces. Therein oligomer or, as the case maybe, polymer molecules are formed directly on the solid surface via a“living”/controlled radical polymerization reaction. According to thestate of the art, prior to the development of the present inventionradical polymerization reactions initiated from solid surfaces were notcontrollable, or could only be controlled with difficulty, with respectto the chain length of the growing polymer chains. According to theinvention, now radical reactions, which begin with appropriatelychemically modified solid surfaces, can be carried out withouttermination, that is they can be controlled in a targeted manner.Therewith the graft branch length can be tailored with simultaneouslymaintaining a narrow chain length distribution; likewise it becomeseasily possible to produce block copolymers as graft moieties.

The advantage of this inventive process is comprised therein, that themethod of the “living”/controlled radical polymerization can be employedupon any solid surface by using initiator groups which are easy to useand widely employable due to their stability, and which have thecharacteristic of making it possible to use the “living”/controlledradical polymerization according to the ATRP-mechanism at temperaturesbelow 120° C., without however simultaneously suffering from thermalpolymerization.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the ¹H-NMR-spectrum of compound (31).

FIG. 2 shows the ¹³C-NMR-spectrum of compound (31).

FIG. 3 shows the ¹H-NMR-spectrum of compound (32).

FIG. 4 shows the ¹³C-NMR-spectrum of compound (32).

FIG. 5 shows the ¹H-NMR-spectrum of compound (33).

FIG. 6 shows the ¹³C-NMR-spectrum of compound (33).

FIG. 7 shows the ¹H-NMR-spectrum of compound (34).

FIG. 8 shows the ¹³C-NMR-spectrum of compound (34).

FIG. 9 shows the FT-lR spectrum of initiator (35).

FIG. 10 shows the FT-lR spectrum of initiator (36).

FIG. 11 shows the FT-lR spectrum of compound (39).

FIG. 12 shows the FT-IR spectrum of the silica gel with the initiator(35) bonded to the surface.

FIG. 13 shows the FT-IR spectrum of the silica gel with the initiator(36) bonded to the surface of the silica gel.

FIG. 14 shows the FT-IR spectrum of the glass beads with the initiator(36) bonded to the surface.

FIG. 15 shows the FT-IR spectrum of the gold colloid with initiator (39)bonded to the surface.

FIGS. 16-18 show the diagram of the thermogravimetric analysis of theSamples 1-3.

FIG. 19 shows the GPC-chromatogram of the poly(methylmethacrylate).

FIG. 20 shows the DSC-curve of the poly(styrene) of first generation onthe silica gel surface.

FIG. 21 shows the FT-IR spectrum of the poly(styrene) of firstgeneration on the silica gel surface.

FIG. 22 shows the diagram of the thermogravimetric analysis of thepoly(styrene) grafted silica gel.

FIG. 23 shows the FT-IR spectrum of the poly(isoprene) coated silicagel.

FIG. 24 shows the DSC-curve of the silica gel covered withpoly(isoprene).

FIG. 25 shows the FT-IR-Spectrum of the glass beads covered withpoly(methylmethacrylate).

FIG. 26 shows the DSC-curve of the poly(styrene) formed in first andsecond generation on the silica gel surface.

FIG. 27 shows the FT-IR spectrum of the poly(styrene) forming the firstand second generation on the silica gel surface.

FIG. 28 shows the FT-IR-spectrum of thepoly(styrene-block-p-tert.-butylstyrene) grafted to the silica gel.

FIG. 29 shows the DSC-curve of thepoly(styrene-block-p-tert.-.butylstyrene) formed on the silica gel.

FIG. 30 shows the GPC-chromatogram of the degrafted poly(styrene) of thefirst generation.

FIG. 31 shows the GPC-chromatogram of the degrafted poly(styrene).

FIG. 32 shows the GPC-chromatogram of the cleavedpoly(methylmethacrylate.

FIG. 33 shows the GPC-chromatogram of the cleaved poly(styrene) of firstand second generation.

FIG. 34 shows the GPC-chromatogram of the cleavedpoly(styrene-block-p-tert.-butylstyrene).

DETAILED DESCRIPTION OF THE INVENTION

The solid substrate can be comprised of any material, could be solid orin porous form, could be in finely divided form, could be of natural orsynthetic origin, or could exhibit a heterogeneous surface structure orheterogeneous surface composition. The only precondition is that theemployed solid already exhibits chemical characteristics on its surfaceor that chemical characteristics can be imparted to it, which permit thebonding of chemical compounds via primary valency bonds; herein the term“primary valency bond” is to be understood as including the entirespectrum of chemical bonds included within the three categories ofcovalent, ionic and mechanical bonds as well as transitions between thethree categories. Solid substrates which already inherently have thenecessary chemical composition for bonding of chemical compounds have ontheir surface, for example, hydroxyl groups. On the other hand it isknown that surfaces of nonpolar materials such as, for example,poly(propylene) or poly(tetrafluoroethylene) can without difficulty becoated or surface modified with reaction participating groups, such ashydroxyl groups, for example by plasma treatment.

Besides hydroxyl groups, examples of further functional groups which arecapable on a substrate surface to form primary valency bonds toinitiators, which can be applied to the surface, include —O—, —SH, —S—,—S—S—, -halogen, —NH₂, —NHR, —NR₂, —NH₃ ⁺, —NH₂R³⁰ , —NHR₂ ⁺, —NO₂, —NO₃⁻, —C≡N, —CO—, —CRH—CO—, —COOH, —COO⁻, —COCl, —CO—O—, —CO—NH—, —SO₃ ⁻,—SO₂Cl, —PO₃ ⁻, —PO₂Cl, —CO—S—, —CS—O—, —C≡C—, —C═—C—, aryl. Therein thesubstituent R can respectively be selected independently from the group:H, alkyl, preferably methyl through propyl, aryl, also substituted,preferably phenyl, also mixed alkyl and aryl. Reactive substratesurfaces can in suitable manner be chemically modified by the inventiveprocess.

This modification of substrate surfaces is inventively carried out bythe following steps:

On a substrate surface to be chemically modified, which is sufficientlyreactive to form primary valency bonds to chemical compounds viachemical reactions (see above), there are bound the chemical compoundswhich in the following are referred to as initiators of general Formula(1) A—L—I. The initiator group I which is present as a component ofA—L—I, and from which the polymer growth proceeds according to theATRP-mechanism, corresponds to C-Z′ according to Formula III of thePatent WO 98/01480 from K. Matyjaszewski et al. The selection of theinitiator group depends upon the desired reaction conditions and themonomer to be polymerized.

In the compounds of general Formula (1) at least one anchor group A, asdefined in greater detail below, must be present, which is in conditionto bond the compound (1) to the surface in the manner of a chemicalprimary valency bond by reacting with the functional groups orfunctionalities situated on the substrate surface. This bond must bestable under the conditions of the respective predetermined reactionconditions for the “living”/controlled radical polymerization.

Further, the bond formation must itself proceed under reactionconditions under which, depending upon the respective initiator group I,from which the polymer growth occurs according to the ATRP-mechanism,this is stable.

For the carrying out of the bonding of the compounds of general Formula(1) A—L—I to the substrate surface, reaction types come intoconsideration through which the linkages can be newly connected. Whethera solvent is necessary, and if so, which solvent is to be employed,depends upon the respective reactants. Further, the selection of processchemicals depends upon the respective reaction type with which thelinkage of the initiator to the substrate surface is carried out.

These preconditions necessary for the suitability or candidacy of thereactive group can be satisfied by a wide range of groups or as the casemay be structural elements. For example the following functional groupscould be mentioned:

Anchor Group A in A—L—I of the general Formula (1) A = OH Halogen SiR³_(y)R⁴ _(z)X_(3−(y+z))*) CR═CR**) CR═CR₂ C≡CR CRO COOR COO⁻ COCl (Br)CO—O—CO—R CH(OH)(OR) C(OR)₃ CO—CH═CR₂ CO—NR₂ C≡N NH—C≡N NH₂ NHR NR₂ NH₃⁺ NH₂R⁺ NHR₂ ⁺ NH—COOR C(NR)—CH═CR₂ NR—NR₂ NR—OH NH—C(NR)—NH₂ CO—NR—NR₂CH═CR—NR₂ CO—N═C═S N═C═O N═C═S O—C≡N S—C≡N NO₃ ⁻ N⁺≡N N═P(Phenyl)₃CH═P(Phenyl)₃ PO₃ ⁻ O—PO₂Cl PO₂Cl COSR CSOR CS—NR₂ CSSR SH SO₃R SO₂R SORSO₃Cl SO₃ ⁻ SO₂Cl SOCl

*) X = halogen, OR⁶, NH₂, with R⁶ as well as R³ and R⁴ = alkyl, alsobranched, preferably methyl, ethyl, also unsaturated, also cycloalkyl,preferably cyclohexyl, also substituted, aryl, preferably phenyl, alsosubstituted, (y + z) ≦ 2 **) R = a substituent, respectivelyindependently selected from the group: H, alkyl, preferably methylthrough propyl, aryl, also substituted, preferably phenyl, also mixedalkyl and aryl; applies for all R in this table, which bear nosuperscript.

Further the anchor group A can be a metallic residue M, with which A—Lbecomes a group in the sense of a metalorganic reagent M—L. Inchemically useful manner with respect to L, as well as directed to thetype of the functional groups on the substrate surface, via which thereaction with the anchor group A═M is to be carried out, M is soselected that, with the reaction partners M—L and the functional groupson the substrate surface, cross-coupling can occur. M—L can therewith bemetalorganic groups with lithium (Murahashi), sodium, magnesium(Grignard, Kumada-Tameo, Corriu), boron (Suzuki-Miyaura), aluminum(Nozaki-Oshima, Negishi), zirconium (Negishi), zinc (Negishi, Normant)cooper or copper-lithium or copper-zinc (Normant, Sonogashira), tin(Migita-Kosugi, Stille), silicon (also variance of Hiyama), mercury,cadmium and silver. For carrying out the cross-coupling it is furthernecessary to employ a suitable catalyst, as well as to match thecharacteristics of the respective functional groups on the substratesurface to be a suitable leaving group as electrophilic reactionpartner. Suitable catalysts, each depending upon metalorganic groupingM—L, include elemental metal or a compound (salt or complex) of themetals Pd(0), Pd(II), Ni(0), Ni(II), Pt(0), Cu(I), Co(II), Co(III),Fe(I), Fe(III), Mn(II). In certain cases mixtures of two catalysts couldalso be mentioned, or the addition of a co-catalyst (for example tin) orcatalyst compounds, which include two metals, such as for exampleLi₂CuCl₄. Preferred are Pd- and Ni-catalysts.

With this type of cross-coupling C—C compounds can be linked, in whichthe C-atoms involved in the bonding are identically or differentlyhybridized. The reaction conditions to be met in the individual casesare set forth in the literature associated with the above indicatedauthor names.

The structural element L present as component of A—L—I can be selectedindependently from the following list 1.-3.:

1. L is a structural element which in accordance with Formula III ofPatent WO 98/01480 of K. Matyjaszewski et al. can have the therespecified and in chemically useful manner, each independently from theother, selected group R¹¹, R¹², R¹³, wherein at least one H or halogencorresponds to A in all three, preferably in two, particularlypreferably however in one of the groups R¹¹, R¹², R¹³ (note: only thegroup definition of R¹¹, R¹², R¹³ correspond to those of the Patent WO98/01480 of K. Matyjaszewski et al.). Besides this, at least one H orhalogen in all three, only in two or also only in one of the groups R¹¹,R¹², R¹³ can be I. Functional groups, which in Patent WO 98/01480 of K.Matyjaszewski et al. are contained within the variability of R¹¹, R¹²,R¹³, can here already exercise the function of anchor groups A or theycan serve for introduction of A.

2. L is a structural element, in which all groups R¹¹, R¹², R¹³(according to Formula III) of Patent WO 98/01480 of K. Matyjaszewski etal.) or two of these groups or even only one group are replaced by

a) oligo(oxyalkylene) with C₁ through C₂₀, also alternating C₁ and C₂groups,

b) oligo(ethyleneimine),

c) oligosiloxanyl with Si₁, through Si₂₀, SiR¹R² with R¹ and R² beingalkyl, preferably methyl, also aryl, preferably phenyl, also mixtures ofalkyl and aryl,

wherein in a) through c) at least one H, in c) at least H or also atleast one aryl, in all three, preferably in two, most preferably howeverin one of the groups R¹¹, R¹², R¹³ is the same as A. Besides this in a)through c) at least one H, or in c) at least one H or one aryl can inall three, only in two or also only in one of the groups R¹¹, R¹², R¹³can be a further I.

3. L is a structural element, in which in the groups R¹¹, R¹², R¹³(according to Formula III) of Patent WO 98/01480 of K. Matyjaszewski etal.) an optional contained group R⁵, which goes beyond the specificationin Patent WO 98/01480, is one of the following groups:

a) oligo(oxyalkylene) with C₁ through C₂₀, also alternating C¹ and C₂groups,

b) oligo(ethyleneimine),

c) oligosiloxanyl with Si₁ through Si₂₀, SiR¹R² with R¹ and R² beingalkyl, preferably methyl, also aryl, preferably phenyl, also mixtures ofalkyl and aryl,

wherein in a) through c) at least one H, in c) at least H or also atleast one aryl, in all three, preferably in two, most preferably howeverin one of the groups R¹¹, R¹², R¹³ is the same as A. Besides this in a)through c) at least one H, or in c) at least one H or one aryl can inall three, only in two or also only in one of the groups R¹¹, R¹², R¹³can be a further I.

The appropriate selection of L offers, via the therein containedfunctional group, the possibility of the cleaving off or separating ofthe polymer layer from the substrate surface.

For the bonding to solid substrates, particularly to those which exhibitOH— groups, and particularly those, which exhibit Si—OH— groups, silylcompounds having the following Formula 2 have been found to work well

X_(3-(y+z))R³ _(y)R⁴ _(z)Si—L—I  (2)

always with (y+z)≦2 wherein X=halogen, OR⁶, NH₂ and R⁶, R³, R⁴=alkyl,also branched, preferably methyl, ethyl, also unsaturated, alsocycloalkyl, preferably cyclohexyl, also substituted, aryl, preferablyphenyl, also substituted, further L=chemical bond or an inorganic ororganic group within widely variable limits as defined above, furtherI=initiator group for the “living”/controlled radical polymerizationaccording to the ATRP-mechanism, specified as above.

The initiator molecule can be bonded to the substrate surface (in thisexample a silicate surface and y=z=0) via the silyl anchor group A:

The silyl anchor group A is, depending on the number of the reactivegroups, tri-, di-, or monofunctional. Preferably chlorine is employed asthe halogen, since a large number of compounds exist and their price isreasonable. The selection of the solvent depends upon the reactantsemployed. With chlorine as halogen the reaction is preferably carriedout in the presence of an ancillary base, for example triethylamine, andin a dry organic solvent.

Besides the above exemplary described coupling or connection of thesolid substrate surface to the initiator, also possible are suchcouplings which can be formed by a sulfide, disulfide, ether, ester,thioester, sulfonate, amide, amine, C—C—, C—N-linkage or by interactionbetween counter ions. These linkages could also be produced throughsubstitution, addition or condensation reactions. The thereforenecessary reactions have long been known in the field of the organicsynthesis, as are the preferred solvents and other process chemicals andprocess parameters.

For the coupling or linkage to solid substrates, especially to such,which exhibit OH— groups, carbonic acid derivatives of Formula (3) havebeen found effective. Therein L and I are specified as above.

Y—CO—L—I  (3)

wherein Y=halogen, preferably chlorine, bromine, OH, OR⁷, whereinR⁷=alkyl, preferably methyl, ethyl, aryl, preferably phenyl, alsosubstituted, aralkyl, preferably benzyl, acyl, aliphatic or aromatic,trialkylsilyl, preferably tri-methylsilyl.

For bonding or linking to semiprecious metals or noble metals, of whichthe solid substrate surface is not functionalized, thiol and disulfideanchor groups of the general Formulas (4) and (5) have been foundeffective.

HS—L—I  (4)

I—L—S—S—L—I  (5)

Therein L and I are specified as above.

The above and hereafter mentioned initiators of type (1)-(6) can includein their structural element L, specified as above, a compound, forexample an ester functionality, which under appropriate conditions canbe cleaved. A cleavable linkage is preferably established on thesubstrate surface in view of the analysis of the formed polymer, whenrequirements are made of the molar mass, the distribution, and thenumber of the formed polymer chains.

As initiators, which are capable of initiating a “living”/controlledradical polymerization according to the ATRP-mechanism on substratesurfaces, there are employed compounds of the general formula

A—L—I  (1).

The components A, L and I contained in (1) are each independentlyselectable from the above provided specifications for A, L, and I.

An advantageous selection from the above specification for A in (1) arethe initiator compounds of Formulas (2)-(6):

X_(3-(y+z))R³ _(y)R⁴ _(z)Si—L—I  (2)

Y—CO—L—I  (3)

HS—L—I  (4)

I—L—S—S—L—I  (5)

═—L—I  (6)

Therein X, Y, R³, R⁴, L, I, y, z are specified as above.

Preferred among the L in (1) in the above specification is a chemicallinkage; alkyl with C₁ through C₂₀, preferably C₁ through C₈; aryl,preferably phenyl, also substituted; aralkyl with the aryl componentpreferably phenyl and with the alkyl component C₁ through C₂₀;

or a structural element, in which as initiators compounds of Formulas(7) through (11) are produced:

Therein R¹, R²=alkyl, preferably methyl, also aryl, preferably phenyl,also mixtures of alkyl and aryl. Therein further n=1-20 and n=1 through20. Further A and I are specified as above.

In selecting preferred I from the above specification in (1), thereresult for example as particularly preferred initiators compounds of theFormulas (12)-(28):

y, z=0, 1, 2, wherein (y+z)≦2

x=1-20

m=1-20

n=1-20

u=0, 1

R¹, R²=definition in siloxane linkage L, specified as above

R³, R⁴=definition of the silyl anchors specified as above

R⁸=H, alkyl, preferably methyl, ethyl

R¹¹, R¹²=independently from each other selectable substituents accordingto Formula III of the Patent WO 98/01480 of K. Matyjaszewski et al.

X=specified as above

Y=specified as above

Z′=transferable atom according to the ATRP-mechanism, of the groupaccording to Patent WO 98/01480 from K. Matyjaszewski et al., preferablyBr, Cl.

Beginning with the ATRP-initiators linked to the solid substratesurface, a “living”/controlled radical polymerization is carried outusing radical polymerizable monomers. Radical polymerizable monomers arepreferably styrene and its derivatives, acrylate, methacrylate,acrylonitrile, however also macromonomers and generally all compoundswith a polymerizable C—C-double bond, wherein various monomers can beemployed as mixtures or sequentially, in order to produce a copolymer orblock copolymer on the solid substrate surface. The oligomer or polymerchains formed in a “living”/controlled radical polymerization reactionon the solid substrate surface can be linear or branched. In a“living”/controlled radical polymerization each chain, started from aninitiator, continues to grow as long as monomers are present in thereaction mixture. Since we are concerned with a “living” polymerization,the chain ends continue to remain active after complete incorporation ofthe monomers, that is, they are capable of further “living”/controlledradical polymerization reactions. For this reason the solid substrateparticles, from out of which the “living”/controlled radicalpolymerization is initiated, are and remain, during the polymerizationand also after the polymerization individual solid substrate particles.

Beginning with the still active chain ends of the polymer chains of thefirst generation, a polymer layer of a second generation can be producedupon the first polymer layer via a renewed “living”/controlled radicalpolymerization. This. polymer layer of second generation can becomprised of polymers or macromonomers species different from thepolymer layer of the first generation, or of a mixture of variousmonomers or macromonomer species or of mixtures of monomers andmacromonomers. The polymer layer of the second generation is linked withthe polymer layer of the first generation through chemical primaryvalency bonds.

Further generations of polymer layers can be added by polymerizationupon the polymer layer of the second generation, in the same manner,depending upon requirements, so that layer systems tailored torequirements can be produced, wherein the linkages between the layersamong each other and between the first layer and the solid substrate,respectively, occur via chemical primary valency bonds.

It is further preferred that the polymer layers can be modified, forexample, by chemical conversion of functional groups of the oligomer orpolymer chains coupled to the solid substrate, using suitable reactants,while maintaining the degree of polymerization.

Herein the functional groups could be in each individual monomer unit,or also the “living” end group. In the appropriate reagents these couldbe low molecular or high molecular compounds or mixtures of the same.

It is further preferred to chemically cross-link the produced solidsubstrate polymer layer into a three dimensional polymer matrix systemby cross-linking polymerization reactions.

A further feature of the invention is oligomers or polymer layers,produced by the inventive process, as well as the initiators of thegeneral Formula (1), for which on the one hand the following Formulas(2)-(28), on the other hand and in particular the Formulas (29)-(39)illustrated in Examples 1-11 are exemplary. The components A, L and Icontained in Formulas (1)-(11) are each independently selectable fromthe above provided specifications for A, L and I.

A—L—I  (1)

X_(3-(y+z))R³ _(y)R⁴ _(z)Si—L—I  (2)

Y—CO—L—I  (3)

HS—L—I  (4)

I—L—S—S—L—I  (5)

═—L—I  (6)

wherein X, Y, R³, R⁴, y, z are specified as above.

Therein R¹, R²=alkyl, preferably methyl, also aryl, preferably phenyl,also mixtures of alkyl and aryl. Therein further n=1-20 and n=1 through20. Further A and I are specified as above.

y, z=0, 1, 2, wherein (y+z)≦2

x=1-20

m=1-20

n=1-20

u=0, 1

R¹, R²=definition in siloxane compound of linkage L, specified as above

R³, R⁴=definition of the silyl anchors specified as above

R⁸=H, alkyl, preferably methyl, ethyl

R¹¹, R¹²=independently from each other selectable substituents accordingto Formula III of the Patent WO 98/01480 of K. Matyjaszewski et al.

X=specified as above

Y=specified as above

Z′=according to the ATRP-mechanism transferable atom of the groupaccording to Patent WO 98/01480 from K. Matyjaszewski et al., preferablyBr, Cl.

With the inventive process, layers or layer systems can be produced,which change the characteristics of the original surface to the extentthat the characteristics are determined only by the coating as such.

Typical surface characteristics are—besides the chemical reactivity—forexample adhesion and permeation characteristics, surface tension,capability for adsorption, optical characteristics such as for examplereflectivity, surface conductivity, appearance, hardness, etc. There arethus countless possible applications for the subject matter of theinvention.

The inventive process can be employed for example

for production of polymer layers on planar or non planar solid substratesurfaces, in order to adjust the physical or as the case may be chemicalcharacteristics for certain utilities such as for example surfaceprotection (abrasion, corrosion), physical interaction with theenvironment (anti-friction, hardness), chemical surface reactivity,photoreactivity, optical characteristics, thermal dynamic stability,etc.

for production of for example porous, oligo or polymer coated materials,in order to targetly adjust the permeation and/or sorption of gases andfluids, for example for purposes of separation of different components,

for production of polymer layer coated solid substrates and polymercoated highly dispersed solids according to the core-shell principle, inorder with them as filler to be able to targetly control a chemicalbinding of the dispersed phase in the surrounding continuous matrix (forexample polymer matrix),

for production of polymer layer coated solids and polymer coated highlydispersed solids, with targeted controllable polymer coating materialsaccording to the core-shell principle, for production of new types ofcomposite systems with processing possibilities above the glasstransition temperature of the polymer coating.

Further application possibilities lie in the field of medicine. By usingthe inventive process the surfaces of implants of natural or syntheticorigin can be so conditioned, that an improved compatibility with bodycells is made possible and therewith a better incorporation of theimplant is achieved. By the application of suitable molecules boundchemically to the polymer onto the surface of implants the rejectionreaction against the implant could be reduced.

The following examples serve to further illustrate the invention.

EXAMPLES Initiators Example 1 Initiator of General Formula (3)

2-Chloro-2-phenyl-acetic acid chloride (29) represents a suitable,easily obtainable initiator of the general Formula (3); it correspondsto the preferred Formula (26) when Z′═Cl, Y═Cl and R¹¹═H.

Example 2 Initiator of General Formula (3)

2-Bromo-2-methylpropionic acid bromide (30) represents a suitable,easily obtainable initiator of the general Formula (3); it correspondsto the preferred Formula (27) when Z′=Br, Y═Br and R¹¹=methyl andR¹²=methyl.

Example 3 Initiator of General Formula (6)

Tetrahydrofuran (THF) is dried, in that it is heated to boiling oversodium wire under reflux condensation. It is distilled immediately priorto use.

Pyridine is dried over KOH and fractionally distilled.4-Allyloxy-4′-hydroxy-biphenyl is produced in accordance with knownliterature [Finkelmann, H.; Lühmann, B.; Rehage, G.; Makromol, Chem.186, 1095 (1985)]. 2-Bromo-2-methylpropionic acid bromide (30) isfractionally distilled in vacuum. Petroleum ether is fractionallydistilled, wherein the fraction with the boiling point between 40° C.and 65° C. is employed. Diethylether is distilled.

2.26 g (10 mmol) 4-allyloxy-4′-hydroxybiphenyl are dissolved in 100 mlabsolute THF. Into this solution is introduced 1 ml (12 mmol) pyridineand the solution is cooled to 0° C. in an ice bath. To this there isthen dropwise added a solution of 1.5 ml (12 mmol)2-bromo-2-methylpropionic acid bromide (30) in 20 ml absolute THF. Aftercompletion of the addition it is warmed to room temperature and forfurther 6 hours stirred while excluding moisture.

The precipitate is filtered and the solvent is removed in vacuum. Theresidue is dissolved or taken up in diethyl ether and the organic phasewashed with 0.5N HCl, NaHCO₃ and water. The organic phase is dried overNa₂SO₄ and the solvent removed in vacuum. After column chromatographicpurification on SiO₂ with petroleum ether/diethyl ether (1/1 v/v) aseluent, the compound (31) was obtained.

Yield: 1.7 g of the initiator (31) Analysis: ¹H-NMR, ¹³C-NMR

FIG. 1 shows the ¹H-NMR-spectrum of compound (31)

FIG. 2 shows the ¹³C-NMR-spectrum of compound (31)

Recording conditions: Solution of the initiator (31) in CDCl₃ with TMSas internal standard.

Example 4 Initiator of General Formula (6)

Dichloromethane is dried over CaH₂, distilled and stored over molecularsieve of 4 Å. Acetic acid ethyl ester is distilled.2-(2-(2-Allyloxy-ethoxy)-ethoxy)-ethanol is produced in accordance withconventional literature [Mitchell, T. N.; Heesche-Wagner, J.; J.Organomet. Chem. 436, 43 (1992)]. The preparation of other chemicals andsolvents is described in the above Example 3.

2.85 g (15 mmol) 2-(2-(2-allyloxy-ethoxy)-ethoxy)-ethanol and 1.6 ml (20mmol) pyridine are dissolved in 150 ml absolute dichloromethane. Thesolution is cooled to 0° C. in an ice bath under exclusion of moisture.To this there is then dropwise added a solution of 2.3 ml (19 mmol)2-bromo-2-methylpropionic acid bromide (30) in 20 ml absolutedichloromethane. After completion of the addition it is warmed to roomtemperature and stirred for additional 6 hours.

The precipitate is filtered off and the solvent is removed in vacuum.The residue is dissolved in acetic acid ethyl ester and the organicphase is washed with 0.5N HCl, NaHCO₃ and water. The organic phase isdried over Na₂SO₄ and the solvent removed in vacuum. After columnchromatographic purification on SiO₂ with acetic acid ethyl ester aseluent the compound (32) is obtained.

Yield: 3.82 g of the initiator (32) Analysis: ¹H-NMR, ¹³C-NMR

FIG. 3 shows the ¹H-NMR-spectrum of compound (32)

FIG. 4 shows the ¹³C-NMR-spectrum of compound (32)

Recording conditions: Solution of the initiator (32) in CDCl₃ with TMSas internal standard.

Example 5 Initiator of General Formula (6)

2-Chloro-2-pheny acetic acid chloride (29) is fractionally distilled invacuum. Triethylamine is dried over CaH₂ and distilled under an inertatmosphere. 10-undecene-1-ol is used without further purification. Thepretreatment of other chemicals and solvents is as described above inExamples 3 and 4.

6 ml (29.8 mmol) 10-undecene-1-ol and 4.6 ml (33 mmol) triethylamine aredissolved in 150 ml dichloromethane. The solution is cooled in an icebath to 0° C. and at this temperature with exclusion of moisture andlight a solution of 4.8 ml (33.1 mmol) 2-chloro-2-phenyl acetic acidchloride (29) in 50 ml absolute dichloromethane is added. Aftercompletion of addition the reaction mixture is warmed to roomtemperature and stirred for additional 6 hours.

The reaction mixture is transferred to a separatory funnel and is washedwith respectively 150 ml 0.5N HCl, NAHCO₃ and distilled water. Theorganic phase is separated, dried over Na₂SO₄ and the solvent is removedin vacuum. The product2-chloro-2-phenyl-acetic-acid-(10′-undecenyl)ester (33) is isolatedafter SiO₂ column chromatographic purification with petroleumether/acetic acid ethyl ester (10/1 v/v).

Yield: 5.7 g of the initiator (33) Analysis: ¹H-NMR, ¹³C-NMR

FIG. 5 shows the ¹H-NMR-spectrum of compound (33)

FIG. 6 shows the ¹³C-NMR-spectrum of compound (33)

Recording conditions: Solution of the initiator (33) in CDCl₃ with TMSas internal standard.

Example 6 Initiator of General Formula (6)

2-Bromo-2-methylpropionic acid bromide (30) is distilled in vacuum. Thepreparation of other chemicals and solvents is described in the aboveExamples 3-5.

The carrying out, work up of the reaction and isolation of the product(34) is performed as described in Example 5. In contrast, instead of(29) 4 ml (32.4 mmol) 2-bromo-2-methylpropionic acid bromide (30) isemployed.

Yield: 6.7 g of the initiator (34) Analysis: ¹H-NMR, ¹³C-NMR

FIG. 7 shows the ¹H-NMR-spectrum of compound (34)

FIG. 8 shows the ¹³C-NMR-spectrum of compound (34)

Recording conditions: Solution of the initiator (34) in CDC1₃ with TMSas internal standard.

Example 7 Initiator of General Formula (2)

Chlorodimethylsilane is distilled with exclusion of moisture. Ethanol isdistilled. Hexachloroplatinic acid-hexahydrate and dimethoxyethane areemployed without further purification. The preparation ofdichloromethane is described in the above Example 4.

5 g (15.5 mmol) of the compound (33) is added to 40 ml (368 mmol)chlorodimethylsilane. With exclusion of moisture a solution of 30 mghexachloroplatinic acidhexahydrate in 0.5 ml dimethoxyethane/ethanol(1/1 v/v) are added and the reaction mixture is stirred at roomtemperature under inert gas overnight.

For work up or recovery the excess chlorodimethylsilane is distilled offand the residue is taken up in 20 ml absolute dichloromethane. Thesolution is filtered over finely powered Na₂SO₄ and the solvent isremoved in vacuum. The initiator (35) is employed without furtherpurification.

The initiator (35) corresponds to the special formula (12), wherein u=1,x=11, y=1, z=1, Z′=Cl, X=Cl, R³=methyl, R⁴=methyl, R¹¹=phenyl and R¹²=H.

Yield: approximately 6 g of the initiator (35) Analysis: FT-IR

FIG. 9 shows the FT-IR spectrum of initiator (35)

Recording technique: transmission spectrum of (35) as film betweenNaCl-windows.

Example 8 Initiator of General Formula (2)

The carrying out and work up of the reaction and the isolation of theproduct (36) is carried out as described in Example 7. In contrastinstead of (33), 4.9 g (15.4 mmol) of 2-bromo-2-methylproponic acid(10′-undecenyl) ester (34) is employed.

The initiator (36) corresponds to the special formula (12) wherein u=1,x=11, y=1, z=1, Z′=Br, X=Cl, R³=methyl, R⁴=methyl, R¹¹=methyl and R12=methyl.

Yield: approximately 5.9 g of the initiator (36) Analysis: FT-IR

FIG. 10 shows the FT-IR spectrum of initiator (36)

Recording technique: transmission spectrum of (36) as film betweenNaCl-windows.

Example 9 Initiator of General Formula (2)

The carrying out and work up of the reaction and the isolation of theproduct (37) is carried out as described in Example 7. In contrast,instead of (33) 1.8 g (4.8 mmol) of 2-bromo-2-methylproponic acid(4′-allyloxybiphenyl-4-yl)ester (31), 20 ml (184 mmol)chlorodimethylsilane and 15 mg hexachloroplatinic acid-hexahydrate in0.25 ml dimethoxyethane/ethanol (1/1 v/v) are employed.

The initiator (37) corresponds to the special formula (16), wherein x=3,y=1, z=1, Z′=Br, X=Cl, R³=methyl, R⁴=methyl, R¹¹=methyl and R¹²=methyl.

Yield: approximately 2 g of the initiator (37)

Example 10 Initiator of General Formula (2)

The carrying out and work up of the reaction and the isolation of theproduct (38) is carried out as described in Example 7. In contrast,instead of (33) 1.7 g (5 mmol) of 2-bromo-2-methylproponicacid(2-(2-(2-allyloxyethoxy)-ethoxy)-ethyl)ester (32), 20 ml (184 mmol)chlorodimethylsilane and 15 mg hexachloroplatinic acid- hexahydrate in0.25 ml dimethoxyethane/ethanol (1/1 v/v) are employed.

The initiator (38) corresponds to the special formula (18), wherein x=3,m=3, y=1, z=1, Z′=Br, X=Cl, R³=methyl, R⁴=methyl, R¹¹=methyl andR¹²=methyl.

Yield: approximately 1.9 g of the initiator (38)

Example 11 Initiator of General Formula (5)

Bis(11-hydroxyundecyl)disulfide is prepared in accordance with knownliterature [Bain, C. B.; Troughton, E. B.; Tao, Y. T.; Evall, Jr.;Whitesides, G. M.; Nuzzo, R. G., J. Am. Chem. Soc. 111, 321 (1989)].N,N-dimethylaminopyridine is employed without further purification. Thepreparation of other chemicals and solvents is described in the aboveExamples 3 and 5.

A solution of 3.2 ml (25.9 mmol) 2-bromo-2-methyl-propionic acid bromide(30) in 20 ml absolute THF is dropwise added under inert gas to asolution of 5.02 g (12.3 mmol) di-(11-hydroxyundecyl)-disulfide, 3.8 ml(27.3 mmol) triethylamine and 12 mg (10 μmol) N,N-dimethylaminopyridinein 100 ml absolute THF. The solution was stirred at room temperature foradditional 2 hours.

Solvent is evaporated in a rotation evaporator and the residue is takenup in diethylether. The organic phase is washed with 50 ml 2N sodiumhydroxide solution and three times with 50 ml distilled water. Theorganic phase is dried over sodium sulfate and the solvent removed invacuum. Column filtration with aluminum oxide (neutral) with petroleumether as eluent produces the product (39) as a whitish, waxy oil. (39)corresponds to the special formula (24) when x=11, Z′=Br, R¹¹=methyl andR¹²=methyl.

Yield: 7.36 g of the initiator (39) Analysis: FT-IR

FIG. 11 shows the FT-IR spectrum of compound (39)

Recording technique: transmission spectrum of the film of the compound(39) between NaCl-windows.

Linkage of the Initiators to Solid Substrate Surfaces Example 12Initiator (30) Bonded to Poly(p-hydroxystyrene-co-divinylbenzene)

Poly(p-hyroxystyrene-co-divinybenzene) is prepared in accordance withknown literature [Spittel, A., Diplomarbeit, Universität Hannover(1991)]. Ethanol is distilled. The preparation of other chemicals andsolvents is described in the above Examples 3 and 4.

5 g poly(p-hyroxystyrene-co-divinylbenzene)-microgel is introduced intoa heated round-bottomed flask and stirred with 200 ml absolutedichloromethane under inert gas for 24 hours. Then 1.4 ml (17.3 mmol)pyridine is added. The reaction mixture is cooled in an ice bath and asolution of 2 ml (16.5 mmol) 2-bromo-2-methylpropionic acid bromide (30)in 20 ml absolute dichloromethane slowly is added dropwise. Aftercompletion of the addition the solution is heated to room temperatureand stirring is continued for additional 12 hours.

The microgel covered with (30) is filtered off and sequentially washedwith respectively 100 ml diethylether, ethanol, ethanol/water (1/1 v/v),ethanol and diethylether. The product is dried in vacuum (10 mbar) at50° C.

Yield: 5.65 g microgel covered with initiator (30), corresponding to3.87 mmol initiator (30) per g microgel

Example 13 Initiator (35) Bond to Silica Gel

Silica gel (ultrasil 3370, Degussa) is dried for 36 hours at 110° C. at10 mbar. Toluene is dried over sodium-wire under reflux. It is distilledoff directly prior to use. The preparation of other chemicals andsolvents is as described in the above Examples 3, 5 and 7.

To a suspension of 3 g silica gel in 200 ml dry toluene 2 ml (14.4 mmol)triethylamine and a solution of 2 g (4.8 mmol) 2-chloro-2-phenyl-aceticacid-(11′-(chlorodimethylsilyl)undecyl)ester (35) in 5 ml dry tolueneare added under inert gas. The reaction mixture is stirred for 24 hoursat room temperature under inert gas.

For work up or recovery the silica gel is separated from the reactionsolvent over a diffuser and subsequently washed in portions withrespectively 150 ml toluene, ethanol/water (1/1 v/v) at pH 3,ethanol/water (1/1 v/v), ethanol and diethylether. The silica gel coatedwith (35) is then dried to constant weight at 30° C. and 10 mbar.

Yield: approximately 3.3 g of silica gel coated with (35), correspondingto 0.24 mmol initiator (35) per g silica gel Analysis: FT-IR

FIG. 12 shows the FT-IR spectrum of the silica gel with the initiator(35) bonded to the surface.

Recording technique: transmission measurement of a film, produced byvaporization of a suspension agent onto a KBr-pressed disk.

Example 14 Initiator (36) Bonded to Silica Gel

The steps of the carrying out and work up or recovery of the initiatorcompound on the solid is described in Example 13.

Starting from Example 13, 5 g of silica gel suspended in 300 ml toluene,3.6 ml (25 mmol) triethylamine and instead of initiator (35)2-bromo-2-methylproponic acid(11′-(chlorodimethylsilyl)undecyl)ester(36) in 10 ml absolute toluene is employed. For the work up, a sequenceof 200 ml toluene, ethanol/water (1/1 v/v) of pH 3, ethanol/water (1/1v/v), ethanol and diethylether is applied.

Yield: approximately 5.5 g with (36) covered silica gel, correspondingto 0.27 mmol initiator (36) per g silica gel Analysis: FT-IR

FIG. 13 shows the FT-IR spectrum of the silica gel with the initiator(36) bonded to the surface of the silica gel.

Recording technique: transmission measurement of a film, which wasproduced by vaporizing a suspension material onto a KBr-pressed disk.

Example 15 Initiator (36) Bonded to Glass Beads

In order to increase the number of reactive silanol groups on thesurface of glass beads (170 mesh), 3 g of glass beads are etched atboiling heat in a 4N sodium hydroxide solution for 4 hours. The glassbeads are filtered off and washed with approximately 250 ml distilledwater. The glass beads are dried for 36 hours in vacuum (10 mbar) at 80°C. These steps for carrying out the recovery of the solid substrate withbound initiator occurs analogously to Example 13.

2 g of the glass beads are suspended in a heated round bottom flask in50 ml absolute toluene under inert gas. To this 1.3 ml (9.4 mmol)triethylamine and 3.92 g (9.5 mmol) of the initiator (36) are added. Thereaction is carried out for 18 hours at room temperature under inertgas.

The glass beads are separated from the reaction solution andsequentially washed with 70 ml toluene, ethanol/water (1/1 v/v), pH 3,ethanol/water (1/1 v/v), ethanol and diethylether. The product is driedfor 48 hours at room temperature in vacuum (10 mbar).

Analysis: FT-IR

FIG. 14 shows the FT-IR spectrum of the glass beads with the initiator(36) bonded to the surface.

Recording technique: transmission measurement of a KBr-pressed disk.

Example 16 Initiator (39) Bonded to Colloidal Gold

Colloidal gold in toluene is produced as described in the literature[Burst, M.; Bethell, D.; Kiely, C. J.; Schiffrin, D. J, Adv. Mater., 7,795 (1995)]. Didodecyldisilfide is produced drawing from the literature[Bain, C. B.; Troughton, E. B.; Tao, Y. T.; Evall, J.; Whitesides, G.M.; Nuzzo, R. G., J. Am. Chem. Soc. 111, 321 (1989)].

To a dispersion of 178 mg (0.9 mmol) colloidal gold (particle diameterapproximately 8 nm) in 750 ml distilled toluene there is slowly added asolution of 135 mg (0.336 mmol) didodecyidisulfide and 60 mg (0.085mmol) of initiator (39) in 80 ml distilled toluene and stirred at roomtemperature for additional 3 hours.

The organic solvent is evaporated to dryness and the residue isintensively washed with ethanol and acetone. Subsequently the product isagain dispersed in toluene and again brought to dryness and the residueis again washed with ethanol and acetone. In total this procedure iscarried out three times.

Yield: 0.205 g with (39) covered, colloidal gold Analysis: FT-IR

FIG. 15 shows the FT-IR spectrum of the gold colloid with initiator (39)bonded to the surface.

Recording technique: transmission spectrum of a KBr-pressed disk.

Example 17 Variation of the Concentration of the Initiator (35) on theSilica Gel Surface

The steps for carrying out and recovering the initiator bonded tosubstrate is described in Example 13. In contrast to Example 13, theemployed ratio of initiator (35) to silica gel is varied (see Table 1).The ratio of initiator (35) to absolute triethylamine is 1 to 3 in allexamples.

TABLE 1 Feed ratio of Initiator (35) to silica gel and the resultingsurface concentration of (35) on the silica gel Sample (35)/silica gel(mmol/g)^(a)) (35) (mmol/g)^(b)) 1 0.27 0.14 2 0.73 0.28 3 1.78 0.30^(a))ratio of initiator (35) to silica gel in the reaction mixture^(b))concentration of initiator (35) on the silica gel surface in theproduct, determined by TGA

Yield: see Table 1, last column Analysis: TGA

FIGS. 16-18 show the diagram of the thermogravimetric analysis of theSamples 1-3.

Analysis conditions: heating under nitrogen atmosphere from 30° C. to550° C., then under air from 550° C. to 750° C., heating rate=20° C. perminute. Therein the weight loss of the sample is detected.

Polymerization With Initiators Example 18 Solution Polymerization ofMethyl Methacrylate at 60° C. in Toluene With Initiator (39)

Methyl methacrylate is dried over CaH₂, distilled at reduced pressure,flushed with argon and stored at −20° C. CuBr is washed withconcentrated acetic acid, water and ethanol.N-(n-butyl)-2-pyridylmethanimine is produced in accordance with knownliterature [Haddleton, D. M.; Jasieczek, C. B.; Hannon, J. J.; Shooter,A. J., Macromolecules 30, 2190 (1997)]. The preparation of the remainingchemicals and solutions is described in the above Examples 3 and 13.

10 ml (94 mmol) methyl methacrylate, 10 ml absolute toluene, 135 mg(0.94 mmol) CuBr and 305 mg (1.9 mmol) N-(n-butyl)-2-pyridylmethanimineare introduced into a Schlenk flask, then degassed 3 times in vacuum andrespectively ventilated with nitrogen. Subsequently 664 mg (0.94 mmol)of the initiator (39) in nitrogen is added. The reaction vessel wasclosed with a septum and the reaction mixture was rapidly heated in anoil bath to 60° C. and maintained at this temperature for 24 hours.

After this time the polymer was filtered over a small, aluminum oxide(neutral) filled column. Distilled THF served as eluent. Afterconcentrating the solution in vacuum the polymer was precipitated indistilled petroleum ether.

Yield: 7.8 g poly(methyl methacrylate) Analysis: GPC

FIG. 19 shows the GPC-chromatogram of the poly(methyl methacrylate).

Chromatographic conditions: Eluent: THF, detection: UV and RI,Calibration: poly(styrene)-standard.

From UV: Mw=12657, Mn=10020, U=0.26; from RI: Mw=13116; Mn=10335,U=0.27.

Example 19 Polymerization of Methyl Methacrylate at 60° C. WithInitiator (30) Bonded to Microgel

The pretreatment of other chemicals and solutions occurs according toExample 18.

In a heated Schlenk flask 1.13 9 of microgel coated with initiator (30)from Example 12 are suspended in 10 ml (94 mmol) methyl methacrylate and10 ml absolute toluene. To this 490 mg (3 mmol)N-(n-butyl)2-pyridylmethanimine are added and the suspension is rinsedfor 10 minutes in argon. Then 148 mg (1 mmol) CuBr are added in weakinert gas counter current and the reaction vessel is closed with aseptum. The polymerization is carried out for 24 hours at 60° C.

The batch is cooled in an ice bath and with THF. The microgel isseparated and extracted in a Soxhlet-Extractor with THF for 24 hours.The product is dried in vacuum (10 mbar) at 50° C. to constant weight.

Yield: 6.83 g poly(methyl methacrylate) grafted microgel

Example 20 Polymerization of tert-Butylacrylate With Initiator (30)Bonded to Microgel

Diphenylether is washed with concentrated H₂SO₄, dried over CaCl₂ anddistilled under reduced pressure. 4,4′-Diheptyl-2,2′-bipyridine isproduced according to known literature [Leduc, M. R.; Hawker, C. J.;Dao, J.; Frechet, J. M. J., J. Am. Chem. Soc., 118, 11111 (1996)].Tert-butylacrylate is dried over CaCl₂ and distilled in vacuum, thenstored under inert gas at 0° C. The preparation of other chemicals andsolutions occurs according to Example 18.

In a heated Schlenk flask 1.13 g of microgel covered with initiator (30)from Example 12 is suspended in 10 ml (68.9 mmol) tert-butylacrylate and10 ml diphenylether. To this 704 mg (2 mmol)4,4′-diheptyl-2,2′-bipyridine is added and the suspension is flushedwith argon for 10 minutes. Then 150 mg (1 mmol) CuBr is added underinert gas counter current and the reaction vessel is closed with aseptum. The polymerization is carried out for 12 hours at 90° C.

The batch is cooled in an ice bath and diluted with THF. The microgel isseparated and extracted in a Soxhlet-Extractor for 24 hours with THF.The product is dried in vacuum (10 mbar) at 50° C. to constant weight.

Yield: 3.34 g poly(tert-butylacryate) grafted microgel

Example 21 Polymerization of Styrene at 120° C. With Initiator (35)Bonded to Silica Gel

Styrene is dried over CaH₂, distilled under reduced pressure, flushedwith argon and stored at −20° C. CuCl is washed with 5N HCl, water andethanol. 2,2′-Bipyridine is recrystallized in distilled petroleum ether.Methanol is distilled. (±)-Propylene carbonate is used withoutpurification.

In a heated Schlenk flask, to 1.1 g of the silica gel covered with (35)from Example 13 are added 150 mg CuCl (1.5 mmol), 480 mg bipyridine (3.1mmol), 8 ml styrene (70 mmol) and 8 ml (+)-propylene carbonate. Byrepeated evacuating and filling with argon the reaction batch is freedfrom oxygen. The polymerization occurs under inert gas and intensivestirring for 24 hours at a temperature of 120° C.

After a predetermined time the batch is cooled in an ice bath in orderto terminate the reaction. The suspension is transferred to centrifugalglasses and the silica gel now covered with poly(styrene) is centrifugedoff. In the centrifuge glasses the silica gel is repeatedly washed withtoluene and then with methanol. In order to free the residue from stillattached Cu-salts, the silica gel is suspended in an Erlenmeyer flask inchloroform and water is added over the suspension. The mixture isstrongly stirred and the aqueous phase is exchanged so long until noblue color can be recognized in the aqueous phase any longer. Theorganic phase is separated from the aqueous phase. Then the organicsuspension agent is substantially removed in vacuum.

The product is dried at 60° C. and 10 mbar to constant weight.

Yield: 2.25 g poly(styrene) grafted silica gel, corresponding toapproximately 1.25 g poly(styrene) per g silica gel Analysis: DSC, FT-IR

FIG. 20 shows the DSC-curve of the poly(styrene) of first generation onthe silica gel surface.

Curve 1 is the DSC-signal, which can be recognized in the first heating.Curve 2 is the DSC-signal, which is obtained during a second heating,after a programmed cooling followed the first heating. In curve 2 onesees the glass transition step of poly(styrene) in the range of betweenapproximately 100° C. and 110° C.

FIG. 21 shows the FT-IR spectrum of the poly(styrene) of firstgeneration on the silica gel surface.

Recording technique: transmission spectrum of a cast film.

Example 22 Polymerization of Styrene at 90° C. With Initiator (35)Bonded to the Silica Gel

The reaction is carried out analogously to the above Example 21, howeverthe reaction temperature is adjusted to 90° C. The recovery of thepoly(styrene) grafted silicon gel occurs in similar manner.

Yield: 820 mg poly(styrene) per g silica gel Analysis: TGA

FIG. 22 shows the diagram of the thermogravimetric analysis of thepoly(styrene) grafted silica gel.

Analysis conditions: heating under nitrogen atmosphere from 30° C. to550° C., then in air from 550° C. to 750° C., heating rate=20° C./min.The weight loss of the sample is detected.

Example 23 Polymerization of Isoprene With Initiator (35) Bonded toSilica Gel

Isoprene is washed with sodium hydroxide solution and water and driedover CaH₂. It is distilled under inert gas and stored under inert gas at−20° C. The pretreatment of other chemicals and solutions is describedin the above Examples 13 and 21.

In the screw lid with submerged agitator under ice cooling 250 mg ofsilica gel covered with (35) is added. Thereto 10 ml (100 mmol) isopreneand 312 mg (2 mmol) 2,2′-bipyridine are added. The reaction mixture isflushed with argon, in order to remove oxygen. Then in weak protectivegas stream 102 mg (1.02 mmol) CuCl is added and the reaction vessel isclosed tightly. Under inert gas the reaction mixture is heated for 14hours at 130° C.

The reaction is cooled in an ice bath and the suspension is transferredto a round bottom flask. To this is added 20 ml toluene and the excessisoprene is removed in vacuum. The silica gel covered withpoly(isoprene) is separated by centrifugation and extracted multipletimes with toluene. The product is dried at room temperature in vacuum(10 mbar) to constant weight.

Yield: 1.5 g poly(isoprene) grafted silica gel, corresponding to 5 gpoly(isoprene) per g silica gel Analysis: FT-IR, DSC

FIG. 23 shows the FT-IR spectrum of the poly(isoprene) coated silicagel.

Recording technique: transmission spectrum of a KBr-pressed disk.

FIG. 24 shows the DSC-curve of the silica gel covered withpoly(isoprene).

In the DSC-curve one sees the glass transition step of thepoly(isoprene) between −57° C. and −50° C.

Example 24 Polymerization of Methyl Methacrylate With Initiator (36)Bonded to Silica Gel

The pretreatment of the employed chemicals and solvents is described inthe above Examples 18 and 20.

Into a heated Schlenk flask 300 mg of,silica gel covered with (36) fromExample 14, 4 ml (37 mmol) methyl methacrylate, 4 ml diphenylether and71 mg (0.2 mmol) 4,4′-diheptyl-2′-bipyridine are added. The solution isflushed with argon for 10 min. Then 14 mg (0.1 mmol) CuBr is added tothe reaction mixture, again flushed with argon and the reaction vesselis closed with a septum. The reaction batch is heated in an oil bath for18 hours at 90° C.

After cooling of the batch in an ice bath, the reaction mixture isdiluted with THF and the described silica gel is separated bycentrifugation. The silica gel is extracted in a Soxhlet-Extractor withTHF.

Yield: 2.49 g poly(methyl methacrylate) grafted silica gel,corresponding to 7.3 g poly(methyl methacrylate) per g silica gel

Example 25 Polymerization of Methyl Methacrylate With Initiator (36)Bonded to Glass Beads

The pretreatment of the employed chemicals and solvents is described inthe above Example 18.

1 g of glass beads covered with (36) from Example 15 is introduced in aheated round bottom flask. To this 2 g (20 mmol) methyl methacrylate,2.5 ml absolute toluene, 30 mg (0.2 mmol) CuBr and 70 mg (0.43 mmol)N-(n-butyl)2-pyridylmethaneamine are added. The reaction mixture isflushed with argon for 10 min. After this, the reaction vessel is closedwith a septum and polymerization is carried out for 18 hours at 90° C.

After the reaction, the excess solvent is removed and the coated glassbeads are washed multiple times with respectively 20ml THF. The productis then extracted with THF in a Soxhlet-Extractor for 48 hours.

Yield: 1.04 g of glass beads grafted with poly(methyl methacrylate),corresponding to 0.04 g poly (methyl methacrylate) per g glass beadsAnalysis; FT-IR

FIG. 25 shows the FT-IR-Spectrum of the glass beads covered withpoly(methyl methacrylate).

Recording Technique: Transmission measurement of a KBr-pressed disk

Production of second polymer generation

Example 26 Formation of a Poly(styrene) Layer Second Generation on theSilica Gel Surface

The pre-treatment of various chemicals and solvents is described inExample 21.

Into a heated Schlenk flask 1 g of the poly(styrene)-silica gel producedin Example 21, 150 mg CuCl (1.5 mmol), 470 mg bipyridine (3 mmol), 10 mlstyrene (87 mmol) and 10 ml (±)-Propylene carbonate are added. Byrepeated evacuation and fill in with argon the reaction batch is freedfrom oxygen. The polymerization occurs under inert gas and intensivestirring for 36 hours at a temperature of 120° C.

The reaction is stopped by cooling in an ice bath. The silica gelcovered with a second poly(styrene) layer is removed from the solutionby centrifugation and washed multiple times with toluene and methanol.In order to remove any remaining Cu-salts, the poly(styrene)-silica gelis suspended in chloroform, covered with water, and the aqueous phase isexchanged until no blue color can be recognized any longer in theaqueous phase. Thereafter, the poly(styrene)-silica gel is filtered offand extracted in a Soxhlet-Extractor for 12 hours with toluene.

The product is dried at 60° C. and 10 mbar until constant weight.

Yield: 2.14 g poly(styrene) grafted silica gel of the second generation,corresponding to approximately 3.75 g poly(styrene) per g silica gelAnalysis: DSC, FT-IR

FIG. 26 shows the DSC-curve of the poly(styrene) formed in first andsecond generation on the silica gel surface.

Curve 1 and curve 2 are obtained in sequential heating curves, whereinsubsequent to the first heating, a programmed cooling off occurs. Inboth curves, the last transition point of poly(styrene) is seen in therange between 105° C. and 110° C.

FIG. 27 shows the FT-IR spectrum of the poly(styrene) forming the firstand second generation on the silica gel surface.

Recording technique: Transmission spectrum of a cast film

Example 27 Formation of Poly(styrene-block-p-tert.-butyl styrene) onSilica Gel Surface

p-Tert.-butyl styrene is dried over CaH₂ and distilled under reducedpressure under inert gas, then stored under inert gas at −20° C. Thepre-treatment of further employed chemicals and solvents is described inthe above examples 20 and 21.

Into a pre-heated Schlenk flask to a suspension of 0.505 g ofpoly(styrene) coated silica gel in 6.4 ml Diphenylether and 6.4 ml (35mmol) p-tert.-butyl styrene are added 72 mg (0.73 mmol) CuCl and 530 mg(1.5 mmol) 4, 4′-diheptyl-2.2′-bipyridine. The reaction mixture isflushed with argon for 10 min., then the polymerization reaction iscarried out for 24 hours at 130° C.

The reaction is stopped by cooling in an ice bath. After diluting thereaction mixture with toluene, the poly(styrene-block-p-tert.-butylstyrene) coated silica gel is separated from the reaction solution bycentrifugation. The solid substrate is washed multiple times withtoluene and subsequently with methanol. In order to remove any remainingCu-salts, the poly(styrene-block-p-ter.-butyl styrene) grafted silicagel is suspended in toluene, covered with water and the aqueous phase isexchanged until no blue color is recognized in the aqueous phase.Thereafter, the poly(styrene-block-p-tert.-butyl styrene)-silica gel isseparated from the organic phase and extracted in a Soxhlet-extractorfor 12 hours with toluene.

Yield: 1.1 g poly(styrene-block-p-tert.-butyl styrene) grafted silicagel Analysis: FT-IR, DSC

FIG. 28 shows the FT-IR-spectrum of the poly(styrene-block-p-tert.-butylstyrene) grafted to the silica gel.

Recording Technique: Transmission spectrum of a cast film.

FIG. 29 shows the DSC-curve of the poly(styrene-block-p-tert.-butylstyrene) formed on the silica gel.

The upper curve and the lower curve are the sequentially obtainedheating curves, wherein following the first heating a programmed coolingoff is carried out. In the lower curve two glass transition temperaturesare clearly to be seen in the area between 100° C. and 105° C. and inthe area between 137° C. and 145° C. The first transition is thepoly(styrene)-block, the second transition is associated with thepoly(p-tert.-butyl styrene)-block.

Polymer Analogous Conversion of Polymer Grafted Substrates Example 28Partial Ester Cleavage of the Poly-(acrylic acid-co-tert.-butyl AcrylicAcid) Grafted Micro-gel

Trifluoroacetic acid is used without purification. The pre-treatment ofdichloromethane is described in the above Example 4.

500 mg of the micro-gel grafted with poly(tert.-butyl acrylate) fromExample 20 is suspended in 20 ml dichloromethane. To this 0.5 ml (6.5mmol) trifluoroacetic acid is added. Under exclusion of moisture, thereaction mixture is stirred at room temperature for 24 hours.

Over a sinterd glass filter, the grafted micro-gel is separated andwashed with ethanol, ethanol/water (1/1 v/v), ethanol and diethylether.The product is dried in vacuum at 60° C. and 10 mbar.

Yield: 443 mg poly(acrylic acid-co-tert.-butyl acrylic acid) graftedmicro gel

Cleavage of the Polymer From the Solid Substrate Surface Example 29Cleavage of the Poly(styrene) From the Silica Gel Surface for Analysisof the Poly(styrene)

p-Toluenesulfonic acid-monohydrate is used without purification.Methanol is distilled. The pre-treatment of toluene is described inExample 13.

500 mg of the poly(styrene) grafted silica gel from Example 21 issuspended in 150 ml toluene. To this suspension are added 100 mgp-toluenesulfonic acid-monohydrate and 10 ml methanol and the reactionmixture is heated to reflux for 16 hours. The poly(styrene)-solution isseparated from the silica gel by centrifugation. The silica gel iswashed with toluene a total of three times and centrifuged, in order toremove any possible poly(styrene) attached to the silica gel.

Yield: 250 mg poly(styrene) Analysis GPC

FIG. 30 shows the GPC-chromatogram of the degrafted poly(styrene) of thefirst generation.

Chromatographic conditions: Eluent: THF, Detection: UV and RI,Calibration: poly(styrene)-standard

From UV: Mw=29499, Mn=18349, U=0.61; from RI: Mw=30766, Mn 21085,U=0.46.

Example 30 Cleavage of the Poly(styrene) From the Silica Gel Surface forAnalysis of the Poly(styrene)

Silica gel grafted with poly(styrene) from Example 22 is used. Thecarrying out and recovery occurs as described in Example 29.

Yield: 190 mg poly(styrene) Analysis: GPC

FIG. 31 shows the GPC-chromatogram of the degrafted poly(styrene).Chromatographic conditions: Eluent: THF, Detection: UV and RI,Calibration: poly(styrene)-standards

From UV: Mw=6748, Mn=3477, U=0.94; from RI: Mw=7624, Mn=3932, U=0.94

Example 31 Cleavage of the Poly(methyl Methacrylate) From the Silica GelSurface

250 mg silica gel grafted with poly(methyl methacrylate) from Example24, 75 ml toluene, 5 ml methanol and 50 mg p-toluenesulfonicacid-monohydrate are used. The carrying out and recovery is the same asin the description in Example 29. The silica gel is washed with THF inplace of toluene.

Yield: 200 mg poly(methyl methacrylate) Analysis: GPC

FIG. 32 shows the GPC-chromatogram of the cleaved poly(methylmethacrylate.

Chromatographic conditions: Eluent: THF, Detection: UV and RI,Calibration: poly(styrene)-standards

From UV: Mw=230031, Mn=137187, U=0.68; from RI: Mw=240377, Mn=146811,U=0.64

Example 32 Cleavage of the First and Second Generation of Poly(styrene)From the Silica Gel Surface

The poly(styrene) grafted silica gel from Example 26 is used. Thecarrying out and recovery occur as described in Example 29.

Yield: 390 mg poly(styrene) Analysis: GPC

FIG. 33 shows the GPC-chromatogram of the cleaved poly(styrene) of firstand second generation.

Chromatographic conditions: Eluent: THF, Detection: UV and RI,Calibration: poly(styrene)-standards

From UV: Mw=116159, Mn=68097, U=0.71; from RI: Mw=119581, Mn=71587,U=0.66

Example 33 Cleavage of the Poly(styrene-block-p-tert.-butyl Styrene)From the Silica Gel Surface

Dioxane and methanol are distilled. The preparation of toluene isdescribed in Example 13.

250 mg of the polymer coated silica gel from Example 27 is suspended ina mixture of 25 ml toluene, 40 ml dioxane and 40 ml 5N sodium hydroxideand heated under reflux for48 hours.

After separation from the aqueous phase, the organic phase isconcentrated in vacuum. The polymer is then precipitated in methanol.The polymer is dissolved again in toluene and the solution iscentrifuged in order to separate any silica gel particles. The remainingsolution is carefully extracted, concentrated in vacuum, then thepolymer is precipitated in methanol. The polymer is separated and driedat 60° C. in vacuum (10 mbar).

Yield: 180 mg poly(styrene-block-p-tert.-butyl styrene) Analysis: GPC

FIG. 34 shows the GPC-chromatogram of the cleavedpoly(styrene-block-p-tert.-butyl styrene).

Chromatographic conditions: Eluent: THF, Detection: UV and RI,Calibration: poly(styrene)-standards

From UV: Mw=203767, Mn=55552, U=2.67; from RI: Mw=196492, Mn=54679,U=2.59

What is claimed is:
 1. Process for producing (i) layers of polymersand/or oligomers or (ii) layer systems of polymers and/or oligomers on asolid substrate surface, comprising the following steps: a) providingand optionally preparing a solid substrate surface, b) bonding to thesolid substrate surface an initiator which includes a group I forinitiation of a reaction which proceeds according to an ATRP-mechanism,c) subsequent to step b), carrying out on the solid substrate surface afirst ATRP-polymerization initiated by the initiator, with radicallypolymerizable (a) monomers, (b) macromonomers, or (c) mixtures thereof,so that a first layer of polymers and/or oligomers is formed on thesolid substrate surface.
 2. Process for producing (i) layers of polymersand/or oligomers or (ii) layer systems of polymers and/or oligomers on asolid substrate surface, wherein an initiator is bonded to the solidsubstrate surface, which initiator serves as initiation site forATRP-polymerization, the initiator includes a group I for initiating areaction which proceeds according to an ATRP-mechanism, and wherein thereaction conditions are so selected, that the polymerization reactionproceeds according to the ATRP-mechanism, and a polymerization reactioninitiated by the initiator is carried out with radically polymerizable(a) monomers, (b) macromonomers, or (c) mixtures thereof, wherein thereaction conditions are so selected, that a polymer and/or oligomerlayer is formed on the solid substrate surface.
 3. Process according toclaim 1 or 2, wherein the initiator is bonded to the substrate surfacevia an anchor group A.
 4. Process according to claim 3, wherein theanchor group A and the group I for initiating a reaction which proceedsaccording to an ATRP-mechanism are linked via a structural element L. 5.Process according to claim 1 or 2, wherein one furtherATRP-polymerization is carried out for providing a second polymer and/oroligomer layer, or a series of further ATRP-polymerizations is carriedout for providing further polymer and/or oligomer layers on the firstlayer.
 6. Process according to claim 1 or 2, wherein the first polymerand/or oligomer layer, or if present, the further polymer and/oroligomer layers are modified by chemical conversion of functional groupsof the polymer chains bonded to the substrate surface, by means ofreaction partners while however maintaineng the degree ofpolymerization.
 7. Process according to claim 1 or 2, wherein theproduced solid substrate/polymer-layer system is cross-linked into athree-dimensional polymer matrix by a cross-linking reaction.